Systems and methods for hydrogen generation from solid hydrides

• US 20050238573A1
• Filed: 04/14/2005
• Published: 10/27/2005
• Est. Priority Date: 04/14/2004
• Status: Abandoned Application

• Current Assignee: Millennium Cell Inc.
• Original Assignee: Millennium Cell Inc.
• Inventors: Wu, Ying, Zhang, Qinglin, Mohring, Richard M.
• Application Number:
  US11/105,549
• Publication Number:
  US 20050238573A1
• Time in Patent Office: Days
• US Class Current: 423/648.100
• CPC Class Codes: B01J 19/2475 Membrane reactors
• CPC Class Codes: B01J 2219/00162 controlling the pressure
• CPC Class Codes: B01J 7/02 by wet methods
• CPC Class Codes: C01B 2203/1604 Starting up the process
• CPC Class Codes: C01B 2203/1609 Shutting down the process
• CPC Class Codes: C01B 3/065 from a hydride
• CPC Class Codes: H01M 8/04208 Cartridges, cryogenic media or cryogenic reservoirs
• CPC Class Codes: H01M 8/04216 characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
• CPC Class Codes: H01M 8/065 by dissolution of metals or alloys; by dehydriding metallic substances
• CPC Class Codes: Y02E 60/36 Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A system is disclosed for hydrogen generation based on hydrolysis of solid chemical hydrides with the capability of controlled startup and stop characteristics wherein regulation of acid concentration, acid feed rate, or a combination of both control the rate of hydrogen generation. The system comprises a first chamber for storing a solid chemical hydride and a second chamber for storing an acidic reagent. The solid chemical hydride is a solid metal borohydride having the general formula MBH₄, where M is selected from the group consisting of alkali metal cations, alkaline earth metal cations, aluminum cation, zinc cation, and ammonium cation. The acidic reagent may comprise inorganic acids such as the mineral acids hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as acetic acid, formic acid, maleic acid, citric acid, and tartaric acid, or mixtures thereof.

Claims

1. A method of generating hydrogen gas, comprising:

providing a fuel in solid form, the fuel being capable of generating hydrogen when brought into contact with a reagent and water;

providing an acidic reagent; and

contacting the acidic reagent with the solid fuel in the presence of water to generate hydrogen gas and a borate by-product.

2. The method of claim 1, wherein the fuel comprises at least one borohydride salt of formula M(BH₄)_n, wherein M is selected from the group consisting of alkali metal cations, alkaline earth metal cations, aluminum cation, zinc cation, and ammonium cation, and n corresponds to the charge of the selected M cation.

3. The method of claim 2, wherein the fuel is combined with a solid stabilizer agent selected from the group consisting of metal hydroxides, anhydrous metal metaborates, and hydrated metal metaborates, and mixtures thereof.

4. The method of claim 2, wherein the molar ratio of water to borohydride is between about 4:

1 to about 5.3;

1.

5. The method of claim 4, wherein the molar ratio of water to borohydride is about 4:

1.

6. The method of claim 1, wherein the fuel comprises a material selected from the group consisting of sodium borohydride, lithium borohydride, potassium borohydride, and calcium borohydride, and mixtures thereof.

7. The method of claim 1, wherein the fuel comprises a material selected from the group consisting of sodium borohydride dihydrate, potassium borohydride trihydrate, and potassium borohydride monohydrate, and mixtures thereof.

8. The method of claim 1, wherein the reagent is in the form of a solid.

9. The method of claim 1, wherein the reagent is in the form of a liquid solution.

10. The method of claim 1, further comprising contacting the fuel with a co-catalyst.

11. The method of claim 10, wherein the co-catalyst comprises a transition metal salt.

12. The method of claim 11, wherein the transition metal salt is a cobalt salt, nickel salt or copper salt.

13. The method of claim 1, wherein the reagent comprises a material selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, maleic acid, citric acid, and tartaric acid.

14. The method of claim 1, wherein the concentration of the acidic reagent is between 0.1 and 17 M.

15. The method of claim 14, wherein the concentration of the acidic reagent is between 1 and 10 M.

16. A method of generating hydrogen, comprising:

providing at least one solid borohydride of formula M(BH₄)_n, wherein M is selected from the group consisting of alkali metal cations, alkaline earth metal cations, aluminum cation, zinc cation, and ammonium cation, and n corresponds to the charge of the selected M cation; and

contacting the solid borohydride with a liquid reagent having a pH lower than about 7 to generate hydrogen.

17. The method of claim 16, wherein the solid borohydride is selected from the group consisting of sodium borohydride, lithium borohydride, potassium borohydride, and calcium borohydride, and mixtures thereof.

18. The method of claim 16, wherein the solid borohydride is selected from the group consisting of sodium borohydride dihydrate, potassium borohydride trihydrate, and potassium borohydride monohydrate, and mixtures thereof.

19. The method of claim 16, wherein the reagent is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, maleic acid, citric acid, and tartaric acid.

20. The method of claim 16, wherein contacting the solid borohydride further comprises contacting with a transition metal salt catalyst.

21. The method of claim 20, wherein the transition metal salt catalyst is a cobalt salt, nickel salt or copper salt.

22. The method of claim 16, wherein the solid borohydride is provided in the form of granules, pellets or powder, or a combination thereof.

23. The method of claim 16, further comprising dispersing the acidic reagent solution prior to contacting the solid borohydride.

24. The method of claim 23, wherein dispersing reduces the size of the droplets of the acidic reagent solution using a mechanism selected from the group consisting of atomizers, spray nozzles, and sparge tubes.

25. The method of claim 16, wherein the molar ratio of H₂O to borohydride is between about 4:

1 to about 5.3;

1.

26. The method of claim 25, further comprising generating a hydrated borate having a molar ratio of H₂O to boron of about 1:

1.

27. A method of producing and controlling the production of hydrogen, comprising:

providing a solid borohydride of formula M(BH₄)_n, wherein M is selected from the group consisting of alkali metal cations, alkaline earth metal cations, aluminum cation, zinc cation, and ammonium cation, and n corresponds to the charge of the selected M cation;

contacting the solid borohydride with an aqueous acidic reagent solution in a reaction chamber to generate hydrogen; and

regulating the rate or concentration of the acidic reagent solution contacting the solid borohydride, to control the rate of hydrogen generation.

28. The method of claim 27, comprising regulating the rate of the acidic reagent solution.

29. The method of claim 27, wherein the reactor temperature is maintained at below about 100°

C.

30. The method of claim 27, further comprising converting the solid borohydride to hydrogen and a borate compound by hydrolyzing the borohydride in the presence of the acidic solution.

31. The method of claim 30, wherein the solid borohydride comprises sodium borohydride.

32. The method of claim 30, wherein the acidic solution comprises hydrochloric acid.

33. The method of claim 30, further comprising cooling the hydrogen.

34. The method of claim 30, wherein the ratio of B/H₂OOin the borate compound is about 1:

2.

35. The method of claim 30, wherein the ratio of B/H₂O in the borate compound is about 2:

5.

36. The method of claim 30, wherein the ratio of B/H₂O in the borate compound is about 1:

1.

37. The method of claim 30, wherein the acidic solution comprises a co-catalyst.

38. The method of claim 37, wherein the co-catalyst is a transition metal salt.

39. A hydrogen gas generation system, comprising:

a first region for containing a solid borohydride;

a second region for containing a reagent solution having a pH of less than about 7; and

at least one gas permeable membrane in contact with the first region, wherein the membrane is capable of allowing hydrogen to pass through the membrane while preventing solid and liquid materials from passing through the membrane.

40. The hydrogen gas generation system of claim 39, further comprising:

a conduit for conveying the reagent solution from the second region to the first region; and

a hydrogen gas outlet in communication with the first region.

41. The hydrogen gas generation system of claim 40, further comprising a control mechanism for regulating the flow of reagent solution from the second region to the first region.

42. The hydrogen gas generation system of claim 41, wherein the control mechanism comprises a pressure control valve.

43. The hydrogen gas generation system of claim 41, wherein the control mechanism comprises a pump.

44. The hydrogen gas generation system of claim 39, wherein at least one of the first and second regions is bounded by a movable material to provide a volume exchanging configuration.

45. The hydrogen gas generation system of claim 39, wherein at least one of the first and second regions is bounded by a flexible material to provide a volume exchanging configuration.

46. The hydrogen gas generation system of claim 39, wherein the solid borohydride has formula M(BH₄)_n, wherein M is selected from the group consisting of alkali metal cations, alkaline earth metal cations, aluminum cation, zinc cation, and ammonium cation, and n corresponds to the charge of the selected M cation.

47. The hydrogen gas generation system of claim 39, wherein the solid borohydride is selected from the group consisting of sodium borohydride, lithium borohydride, potassium borohydride, and calcium borohydride, and mixtures thereof.

48. The hydrogen gas generation system of claim 39, wherein the solid borohydride is selected from the group consisting of sodium borohydride dihydrate, potassium borohydride trihydrate, and potassium borohydride monohydrate, and mixtures thereof.

49. The hydrogen gas generation system of claim 39, wherein the reagent solution comprises an acid selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, maleic acid, citric acid, and tartaric acid.

50. A hydrogen gas generation system comprising:

a fuel chamber for storing a solid borohydride having formula M(BH₄)_n, wherein M is selected from the group consisting of alkali metal cations, alkaline earth metal cations, aluminum cation, zinc cation, and ammonium cation, and n corresponds to the charge of the selected M cation;

a reagent chamber for storing an acidic reagent solution;

at least one gas permeable membrane provided in contact with the fuel chamber to allow hydrogen to pass through the gas permeable membrane while preventing solid and liquid materials from passing through the gas permeable membrane;

a fuel conduit for conveying the acidic reagent solution from the reagent chamber to the fuel chamber; and

a control mechanism for regulating the flow of acidic reagent solution from the reagent chamber to the fuel chamber.

51. The hydrogen gas generation system of claim 50, wherein at least one of the fuel chamber and the reagent chamber comprises a flexible material.

52. The hydrogen gas generation system of claim 50, wherein the acidic reagent solution comprises an acid selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, maleic acid, citric acid, and tartaric acid.

53. The hydrogen gas generation system of claim 50, wherein the control mechanism is a pressure control valve or a pump.

54. The hydrogen gas generation system of claim 50, wherein the solid borohydride is provided in a form selected from the group consisting of pellets, granules and powder.

55. The hydrogen gas generation system of claim 50, wherein the solid borohydride contains less than about 50% by weight water.

56. The hydrogen gas generation system of claim 50, wherein the solid borohydride is sodium borohydride dihydrate and the acidic reagent solution comprises hydrochloric acid.

57. The hydrogen gas generation system of claim 50, wherein the system is connected to a fuel cell.

58. A hydrogen gas generation system, comprising:

a first chamber for storing solid sodium borohydride;

a second chamber for storing a hydrochloric acid solution; and

a control means for regulating the rate of contact between the solid sodium borohydride and the hydrochloric acid solution to allow conversion of the sodium borohydride to generate hydrogen gas.

59. The hydrogen gas generation system of claim 58, further comprising at least one gas permeable membrane provided in contact with the first chamber, to allow hydrogen to pass through the gas permeable membrane.

60. The hydrogen gas generation system of claim 58, wherein the second chamber further comprises a transition metal salt catalyst.

61. The hydrogen gas generation system of claim 60, wherein the transition metal salt catalyst is a cobalt salt, nickel salt or copper salt.